CN111600056A - Preparation method of energy storage composite material structure battery - Google Patents

Preparation method of energy storage composite material structure battery Download PDF

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Publication number
CN111600056A
CN111600056A CN202010411239.3A CN202010411239A CN111600056A CN 111600056 A CN111600056 A CN 111600056A CN 202010411239 A CN202010411239 A CN 202010411239A CN 111600056 A CN111600056 A CN 111600056A
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energy storage
battery
preparing
electrode plate
composite material
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CN111600056B (en
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郭子月
吴海宏
王朝阳
周应国
蒋爱云
黄明
张洛明
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Zhengzhou Fanxian New Material Technology Co ltd
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Zhengzhou Fanxian New Material Technology Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/116Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/04Construction or manufacture in general
    • H01M10/045Cells or batteries with folded plate-like electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10Primary casings; Jackets or wrappings
    • H01M50/131Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method of a battery with an energy storage composite material structure, which comprises the following steps: (1) preparing electrode slurry, (2) coating the electrode slurry on a current collector, (3) drying, rolling and slicing the coated current collector to prepare an electrode plate, (4) placing the electrode plate on two sides of a diaphragm to perform Z-shaped lamination to prepare a cell, (5) preparing a shell by using prepreg and foam materials, then forming a sandwich structure in the shell in which the cell is placed, (6) performing hot-pressing composite molding by using a molding press, (7) injecting electrolytic liquid, and (8) sealing and testing. The battery prepared by the method integrates energy storage and structure, reduces the weight of the energy storage element while keeping the original power density, increases the space utilization rate, provides good mechanical property, increases the explosion resistance of the energy storage element when the energy storage element is pressed or pulled, and improves the safety of the energy storage element.

Description

Preparation method of energy storage composite material structure battery
Technical Field
The invention belongs to the field of energy storage materials, and particularly relates to a preparation method of a battery with an energy storage composite material structure.
Background
With the rapid development of mobile power technologies such as portable electronic devices and electric vehicles, energy storage systems with higher weight and volume efficiency are also sought. The traditional energy storage system has large volume, heavy weight, poor corrosion resistance, easy damage and relatively short service life, and is greatly limited in application in industry. In recent years, a new research field, namely a structural energy storage composite material, is developed by the multifunctional composite material, the structural energy storage composite material is a material integrating structure and energy storage, the excellent mechanical property of the composite material and the energy storage property of the energy storage material can be combined into a single structure, and the weight and the volume of an energy storage element can be obviously reduced.
Disclosure of Invention
The invention aims to provide a structural battery aiming at the defects of large volume, heavy weight, poor pressure resistance and the like of the traditional energy storage element, the battery integrates energy storage and structure, reduces the weight of the energy storage element while keeping the original power density, increases the space utilization rate, provides good mechanical property, increases the explosion resistance of the energy storage element when the energy storage element is pressed or pulled, and improves the safety of the energy storage element.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a battery with an energy storage composite material structure comprises the following steps:
(1) preparing electrode slurry: mixing the active material, the conductive agent and the binder according to the mass ratio of 9:0.5:0.5, and then adding the solvent and fully stirring to uniformly mix the active material, the conductive agent and the binder;
(2) coating: coating the uniformly mixed electrode slurry on a current collector to prepare a positive electrode plate and a negative electrode plate;
(3) drying, rolling and slicing: putting the coated positive electrode plate and negative electrode plate into a vacuum drying oven for drying, then rolling, and finally shearing into electrode plates with proper sizes;
(4) preparing an electric core: the positive electrode plate and the negative electrode plate are symmetrically arranged on two sides of the diaphragm, and the Z-shaped layers are laminated to form a battery cell which comprises the positive electrode plate, the negative electrode plate, the diaphragm, a positive electrode pin and a negative electrode pin;
(5) preparing a sandwich structure: preparing a shell by using prepreg and foam material, and then putting the prepared battery cell into the shell to form a sandwich structure;
(6) curing and forming: placing the assembled sandwich structure in a molding press for curing and molding;
(7) electrolyte injection: placing the cured and molded structure in a glove box and injecting electrolyte;
(8) sealing and testing: after the electrolyte is injected, the injection port is sealed, and the electrochemical performance of the electrolyte is tested by using an electrochemical workstation.
Further, in the step (2), the current collector is 4mol/L H for aluminum foil or nickel foil with the thickness of 0.01mm2SO4Vacuum corroding in the solution at 25 deg.C for 30 min.
Further, in the step (2), the electrode slurry is coated on the current collector to a thickness of 50-300 μm.
Further, the rolling pressure in the step (3) is 35 MPa.
Further, in the step (5), a carbon fiber prepreg or a glass fiber prepreg is used as the prepreg, and preferably, a carbon fiber prepreg is used.
Further, the thickness of the carbon fiber prepreg is 0.02 mm.
Further, the carbon fiber prepreg is composed of carbon fiber woven cloth and epoxy resin.
Further, the specific manufacturing method of the sandwich structure in the step (5) comprises the following steps: placing a rectangular frame around the prepared battery cell, wherein the thickness of the frame is equal to that of the battery cell in the Z-shaped lamination direction, and prefabricating a liquid injection hole in front of a foam frame; and then laying layers on the upper surface and the lower surface of the cell in the Z-shaped lamination direction by using 0.02mm carbon fiber prepreg to form an upper panel and a lower panel, wherein the upper panel and the lower panel are formed by combining the foam frame and the cell in the Z-shaped lamination direction by using the carbon fiber prepreg, so that the whole preform with a sandwich structure is formed.
Further, the curing and forming in the step (6) specifically comprises the following steps: placing the sandwich structure assembled in the step (5) on a molding press, and setting the pressure of the molding press to be 0.1 MPa; raising the temperature of the molding press to 85 ℃, and keeping the temperature for 10 min; and raising the temperature of the molding press to 120 ℃, preserving the heat for 15min, and taking out after the molding press is naturally cooled.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the structural battery composite material shell, the ultrathin carbon fiber prepreg is adopted for layering, resin can be fully soaked among carbon fibers during curing and forming, and the cured and formed composite material shell has fewer defects and better mechanical property.
2. According to the invention, the ultrathin carbon fiber prepreg is directly layered on the battery core, so that the carbon fiber prepreg and the battery core are directly compounded into a whole, and the battery has better mechanical performance, and a battery sheet is not embedded in a composite material sandwich plate to prepare a structural battery, so that unnecessary load is reduced. The structural battery prepared by the method can keep a complete shape under the load of 1200N, does not generate cracks and electrolyte overflow phenomena, and still has good charge and discharge performance.
Drawings
FIG. 1 is a flow chart of a method for manufacturing a battery with an energy storage composite structure according to the present invention;
FIG. 2 is a schematic structural diagram of an electrode plate of a battery with an energy storage composite material structure according to the invention;
fig. 3 is a schematic structural diagram of a cell of the energy storage composite material structure battery of the invention;
FIG. 4 is a schematic structural diagram of a battery with an energy storage composite structure according to the present invention;
in the figure: 1. an electrode pin; 2. riveting; 3. a current collector; 4. electrode paste; 5. a positive electrode pin; 6. a negative electrode pin; 7. a positive electrode plate; 8. a diaphragm; 9. a negative electrode plate; 10. a liquid injection hole; 11. a lower panel; 12. a frame; 13. and a top panel.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
The embodiment provides a preparation method of a battery with an energy storage composite material structure, and referring to fig. 1, the preparation method comprises the following specific steps:
(1) preparing electrode slurry: mixing the active material, the conductive agent and the binder according to the mass ratio of 9:0.5:0.5, adding a proper amount of solvent, and uniformly stirring; in the embodiment, the activated carbon, the conductive carbon black and the PVDF are mixed according to the mass ratio of 9:0.5:0.5, and then an appropriate amount of NMP solution is added to be fully stirred, so that uniformly mixed sticky slurry is obtained.
(2) Coating: coating the uniformly mixed electrode slurry on a current collector 3; this example uses an aluminium foil with a thickness of 0.01mm as current collector, which is placed under vacuum at 25 ℃ with 4mol/L H before coating2SO4The solution was etched for 30min, and the electrode slurry was coated on an aluminum foil to a thickness of 200 μm. The aluminum foil current collector adopted for preparing the electrode plate is further corroded by chemical reagents, and the surface of the current collector is provided with an uneven structure, so that the electrode active material and the current collector are bonded more firmly.
(3) Drying, rolling and slicing: putting the coated electrode slice into a vacuum drying oven for drying, then rolling, and finally shearing into an electrode slice with a proper size; in the embodiment, the coated electrode slice is placed in a vacuum drying oven for vacuum drying for 12 hours at the temperature of 120 ℃; placing the dried electrode slice on a roller press, and pressing by adopting 35MPa pressure to ensure that the surface electrode slurry 4 and the current collector 3 are tightly adhered together; the electrode sheet is cut to an appropriate size as needed, and the electrode pin 1 and the current collector 3 are riveted together with the rivet 2 on the electrode sheet, as shown in fig. 2. The electrode pin 1 is a copper sheet with the thickness of 0.1 mm.
(4) Preparing an electric core: placing the positive plate and the negative plate symmetrically on two sides of the insulating diaphragm, and laminating the Z-shaped layers to form a battery cell as shown in figure 3; the battery cell comprises a positive electrode pin 5, a negative electrode pin 6, a diaphragm 8, a positive electrode plate 7 and a negative electrode plate 9; in the embodiment, the prepared positive electrode plate 7 and the negative electrode plate 9 are folded in a Z shape and then are symmetrically arranged on two sides of the diaphragm 8; the membrane 8 used in this example was a cellulose membrane TF40-30, having a thickness of 30 μm and a porosity of 49%.
(5) Preparing a sandwich structure: prepare the casing with preimpregnation material and foam material, put into the casing with the electric core that prepares and constitute sandwich structure, the concrete process is: placing a rectangular frame 12 (rectangular foam) around the prepared battery core, wherein the thickness of the foam is equal to that of the battery core in the Z-shaped lamination direction, and prefabricating a liquid injection hole 10 on the frame 12; and then laying layers on the upper surface and the lower surface of the cell Z-shaped lamination direction by using carbon fiber prepreg with the thickness of 0.02mm to form an upper panel 13 and a lower panel 11, wherein the upper panel 13 and the lower panel 11 formed by combining the frame 12 and the cell Z-shaped lamination direction are completely covered by the carbon fiber prepreg. Thereby forming an integral preform of a sandwich construction.
(6) Curing and forming: placing the assembled sandwich structure in a molding press for curing and molding; in the embodiment, the sandwich structure is placed in a molding press, the pressure of the molding press is adjusted to 0.1MPa, the temperature of the molding press is firstly increased to 85 ℃, and the temperature is kept for 10 min; and raising the temperature of the molding press to 120 ℃, preserving the heat for 15min, closing the molding press, naturally cooling and taking out to obtain the shell shown in figure 4.
(7) Electrolyte injection: placing the cured and molded shell in a glove box, and injecting electrolyte into the glove box; in this embodiment, the case body formed by curing is placed in a glove box, and the organic electrolyte DLC 301 is injected from the injection hole 10 under vacuum.
(8) Sealing and testing: after the electrolyte is injected, the liquid injection port is sealed, and an electrochemical workstation is used for testing the electrochemical performance of the liquid injection port; in the embodiment, after the liquid injection is finished, the liquid injection hole 10 is sealed by an explosion-proof plug in a glove box; the structural cell was then removed and tested for electrochemical performance using an electrochemical workstation.
Example 2
Unlike the preparation method of example 1, the current collector of this example uses 0.01mm nickelThe foil was vacuum-sealed at 25 ℃ with 4mol/L H2SO4Etching the solution for 30 min.
Example 3
Different from the preparation method of the embodiment 1, the embodiment adopts a porous PP diaphragm as an insulating diaphragm, and the positive electrode sheet 7, the negative electrode sheet 9 and the diaphragm 8 are wound into a cylindrical battery cell.
Example 4
Different from the preparation method of the embodiment 1, in the embodiment, the glass fiber prepreg is directly layered on the upper surface and the lower surface of the Z-shaped lamination direction formed by combining the battery core and the foam frame 12, and then the structural battery is prepared by mould pressing, curing and molding.
Example 5
Different from the preparation method of the embodiment 1, in the embodiment, the ion electrolyte is injected into the structural battery after the die pressing solidification through the injection hole 10, and then the ion electrolyte and the positive and negative electrode plates form the energy storage structural battery.
Example 6
Different from the preparation method in embodiment 1, in this embodiment, activated carbon on an electrode sheet is replaced by a metal oxide, so that the activated carbon and ions in an ionic electrolyte undergo an oxidation-reduction reaction to form pseudo-capacitor energy storage, and then a battery core is prepared.
Comparative example 1
Different from the preparation method in the embodiment 1, in the step (5), carbon fiber prepregs with different thicknesses, such as 0.05mm, 0.10mm, 0.20mm, 0.30mm and the like, are adopted to lay layers on the upper surface and the lower surface of a Z-shaped structure formed by combining an energy storage cell and a foam frame with the same thickness, and then the layers are molded, cured and formed, so that the prepared structural battery can bear the mechanical properties as shown in the following table 1 under normal operation.
TABLE 1 maximum bearing pressure of shells made of carbon fiber prepregs of different thicknesses
Prepreg thickness (mm) Energy storage property of battery Withstand maximum pressure (N)
0.02 Good effect 1200
0.05 Good effect 1100
0.10 Good effect 950
0.20 Good effect 750
0.30 Good effect 500
Comparative example 2
Different from the preparation method of the embodiment 1, in the step (5), in this embodiment, a shell is prepared by performing composite curing molding on a carbon fiber ultrathin prepreg with a thickness of 0.02mm and foam, and then the energy storage battery core is placed in the shell after curing of the carbon fiber and the foam, and is sealed after the electrolyte is injected inwards. The maximum pressure that the carbon fiber structure battery prepared in this way can bear compared with the maximum pressure that the carbon fiber structure battery can bear after being directly layered on the energy storage battery core is shown in table 2.
TABLE 2 maximum bearing pressure of the shells of the different forming methods
Molding method Prepreg thickness (mm) Energy storage property Withstand maximum pressure (N)
Spreading layer solidification directly on electric core 0.02 Good effect 1200
First solidified and then embedded into electric core 0.02 Good effect 700
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. A preparation method of a battery with an energy storage composite material structure is characterized by comprising the following steps:
(1) preparing electrode slurry: mixing the active material, the conductive agent and the binder according to the mass ratio of 9:0.5:0.5, and then adding the solvent and fully stirring to uniformly mix the active material, the conductive agent and the binder;
(2) coating: coating the uniformly mixed electrode slurry on a current collector to prepare a positive electrode plate and a negative electrode plate;
(3) drying, rolling and slicing: putting the coated positive electrode plate and negative electrode plate into a vacuum drying oven for drying, then rolling, and finally shearing into electrode plates with proper sizes;
(4) preparing an electric core: the positive electrode plate and the negative electrode plate are symmetrically arranged on two sides of the diaphragm, and the Z-shaped layers are laminated to form a battery cell which comprises the positive electrode plate, the negative electrode plate, the diaphragm, a positive electrode pin and a negative electrode pin;
(5) preparing a sandwich structure: preparing a shell by using prepreg and foam material, and then putting the prepared battery cell into the shell to form a sandwich structure;
(6) curing and forming: placing the assembled sandwich structure in a molding press for curing and molding;
(7) electrolyte injection: placing the cured and molded structure in a glove box and injecting electrolyte;
(8) sealing and testing: after the electrolyte is injected, the injection port is sealed, and the electrochemical performance of the electrolyte is tested by using an electrochemical workstation.
2. The method for preparing the battery with the energy storage composite material structure according to claim 1, wherein in the step (2), the current collector is 4mol/L H for aluminum foil or nickel foil with the thickness of 0.01mm2SO4Vacuum corroding in the solution at 25 deg.C for 30 min.
3. The method for preparing a battery with an energy storage composite structure according to claim 1, wherein in the step (2), the electrode slurry is coated on the current collector to a thickness of 50-300 μm.
4. The method for preparing the battery with the energy storage composite material structure according to claim 1, wherein the rolling pressure in the step (3) is 35 MPa.
5. The method for preparing the energy storage composite material structure battery according to claim 1, wherein the prepreg in the step (5) is a carbon fiber prepreg or a glass fiber prepreg.
6. The method for preparing the battery with the energy storage composite material structure according to claim 1, wherein the specific manufacturing method of the sandwich structure in the step (5) comprises the following steps: placing a rectangular frame around the prepared battery cell, wherein the thickness of the frame is equal to that of the battery cell in the Z-shaped lamination direction, and prefabricating a liquid injection hole in front of a foam frame; and then laying layers on the upper surface and the lower surface of the cell in the Z-shaped lamination direction by using 0.02mm carbon fiber prepreg to form an upper panel and a lower panel, wherein the upper panel and the lower panel are formed by combining the foam frame and the cell in the Z-shaped lamination direction by using the carbon fiber prepreg, so that the whole preform with a sandwich structure is formed.
7. The preparation method of the battery with the energy storage composite material structure according to claim 1, wherein the curing and molding in the step (6) comprises the following specific steps: placing the sandwich structure assembled in the step (5) on a molding press, and setting the pressure of the molding press to be 0.1 MPa; raising the temperature of the molding press to 85 ℃, and keeping the temperature for 10 min; and raising the temperature of the molding press to 120 ℃, preserving the heat for 15min, and taking out after the molding press is naturally cooled.
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